Soaps and other perfumed compositions containing dihydroterpinyl acetate



United States Patent 'SOAPS AND OTHER PERFUNIED COL [POSITIONSCONTAINING DIHYDROTERPINYL ACETATE Alphonse T. Fiore, Teaneck, Garry C.Kitchens, Packanack Lake, and Harry C. Saunders, Nutley, N.J., assignorsto The Givaudan Corporation, New York, N .Y., a corporation of NewJersey No Drawing. Application July 12, 1956 Serial No. 597,359

3 Claims. (Cl. 167-94) This invention relates to soaps, such as toiletsoap, and other perfumed compositions containing dihydroterpinylacetate.

An object of this invention is to provide a toilet soap having thefollowing odor qualities: good stability, freshness and naturalness (asopposed to a chemical odor).

Another object is to provide a toilet soap having an odor which is cleanand pleasant such as is obtained from the ester components of importantnatural soap odorants, e.g., lavender oil, petitgrain oil, and bergamotoil, and yet not having the roughness and undesirable pine-likecharacter associated with synthetic esters.

Another object of this invention is to furnish perfumed compositionscontaining a low-cost readily available synthetic ingredient whichresembles the oils of bergamot and petitgrain.

Other objects of our invention will become apparent from the followingdescription.

We have attained the foregoing and other objects by incorporatingdihydroterpinyl acetate into toilet soap and other perfumedcompositions. We have found that amounts of dihydroterpinyl acetate fromabout 0.02 to 1.5% by weight of the total soap give satisfactory resultsand that amounts from 0.1 to 0.6% on the same basis give excellentresults.

In using dihydroterpinyl acetate as a substitute or extender for oil ofpetitgrain it has been found that the acetate can be used up to andincluding 40% by weight of the petitgrain oil-dehydroterpinyl acetatemixture.

Artificial 'bergamot oils can be made by using from 5 to 75% by weightof di'hydroterpinyl acetate on the basis "of the total mixture. Weprefer to use amounts from 40 to 60% on the same basis.

Artificial oil of petitgrain containing from 5 to 65% by weight ofdihydroterpinyl acetate on the basis of the total mixture can be made.However, We prefer to use amounts from 30 to 45% on the same basis.

In using our novel perfume ingredient the usual practices of theperfumer may be employed. For this .reason specific instructionsconcerning the method of formulating toilet soap and other perfumedcompositions containing dihydroterpinyl acetate are unnecessary here.

Dihydroterpinyl acetate has already been described in the literature. Tothe best of our present knowledge it was first described in 1910 by M.A. Bhal and M. A. Heller in Compt. rend, 150, 1762-65.

However, in spite of the fact that dihydroterpinyl acetate has alreadybeen known for over 45 years and the fact that terpinyl acetate has beenknown for a long time for its olfactory properties, no one until nowrecognized the unique olfactory properties of dihydroterpinyl acetate.It may well be that the reason for this omission stems from the factthat the closely-related linalyl acetate is weakened in odor qualitieswhen it is hydrogenated. It was therefore surprising to us that we foundthat the odor of dihydroterpinyl acetate is not only as strong as thatof terpinyl acetate but the Patented June 2, 195.9

Specific gravity, 25 C./25 C. 09328-09337 Refractive index, 20 C.1.4493-1.4495

Purity percent.. -100 EXAMPLE I Soap cakes were made as follows:

Twenty grams of standard No. 1 soap pellets and 10.1 gram of perfumingagent were milled together in a Coors No. 522- r porcelain mortar untilthey were reduced to a fine homogeneous powder. Two grams of distilledwater were added and the mixture was milled again to a plastic mass. Thesoap thus prepared was charged into a cylindrical tableting die whichwhen pressed by a hand arbor-press produced a soap cake 3.8 cm. indiameter and 2.0 cm. thick. In separate cakes made as just described wasincorporated the same specifled portions of dihydroterpinyl acetate,terpinyl acetate and linalyl acetate. The cakes were then exposed to airand daylight indoors for a period of 6 months and examined about once amonth.

The cake containing the dihydroterpinyl acetate maintained a strong,fresh odor during the entire period. The cake containing the terpinylacetate weakened after two months and faded completely after threemonths. The cake containing the linalyl acetate turned rancid or soursmelling after two months.

EXAMPLE II A soap perfume was formulated using dihydroterpinyl acetateas an ingredient. The formula is as follows:

Soap perfume N0. 1

Soluble resin Styrax (10% in diethyl phthalate)- 8 This perfume wasincorporated in milled toilet soap at the rate of 1% in the same manneras described in Example I. It covered the odor of the soap well and gavea pleasant refreshing odor to the soap.

EXAMPLE III Another soap perfume was formulated containing a,

larger proportion of dihydroterpinyl acetate. is as follows:

Its formula Soap perfume N0. 2

This perfume was incorporated in soap at the rate of 1% in a manner asdescribed in Example I and found to give a good cover to the soap odorand a pleasant clean odor.

EXAMPLE IV Compositions containing oil of petitgrain and 10, 20, 30, 40,50, 60 and 70% dihydroterpinyl acetate by weight of the total mixturewere prepared. Similar series containing oil of petitgrain and othersynthetic extenders such as terpinyl acetate and nopyl acetate (6,6-dimethylbicyclo-[1,1,31-hept-2-ene-2 ethyl acetate) were prepared.

The petitgrain mixtures containing the other synthetic extenderspossessed a distracting piney note which was not evident in thepetitgrain mixture containing dihydroterpinyl acetate.

Those petitgrain mixtures, containing dihydroterpinyl acetate had morerealistic petitgrain oil odor than the mixture containing the otherpetitgrain extenders at like concentrations.

EXAMPLE V An artificial bergamot was formulated using 70% ofdihydroterpinyl acetate as the main ester component. Following is itsformula:

Bergamot type Dihydroterpinyl acetate 600 Oil sweet orange cold pressedCalifornia 30 Methyl benzoate 20 N-decanal (10% in diethyl phthalate) 3Camphene 16 Geranyl formate 60 Coumarin crystals N.F. 2p-Isopropylacetophenone 26 Terpineol 40 2-methylundecanal-1 (10% indiethyl phthalate) 1 Peppermint rectified oil 5 v 4 Soluble resingalbanum 10% Estragon oil 10% in diethyl phthalate) 14 Bay leaves oil 2Lemon oil California 3 'y-Undecalactone (10% in diethyl phthalate) lSoluble resin labdanum (10% in diethyl phthalate) 2 Soluble resinolibanum 5 Benzaldehyde (1% in diethyl phthalate) 20 EXAMPLE VI Anartificial oil of petitgrain was formulated. The following is theformula:

Dihydroterpinyl acetate 200 Dipentine 60 Camphene 40 Myrcene 24Citronellol 10 Geranyl acetate 20 Methyl anthranilate 43-cyclohexylpropanone-2 l6 Furfural 1 N-decanal (10% in diethylphthalate) 2 Amyl benzoate 8 Bay leaves oil 1.5 Thyme oil white 1.5 Rueoil 2.5 p-Cresyl acetate 1.5 Fennel oil sweet 1 While we have describedour invention in detail in its preferred embodiment, it will be obviousto those skilled in the art, after understanding our invention, thatvarious changes and modifications may be made therein without departingfrom the spirit or scope thereof. We aim in the appended claims to coverall such modifications and changes.

We claim:

1. Toilet soap containing a minor amount of dihydroterpinyl acetatesufficient to impart to said soap odor stability, freshness andnaturalness.

2. Toilet soap, containing from about 0.02% to about 1.5% by weight ofdihydroterpinyl acetate, said soap being characterized by odorstability, freshness and naturalness imparted thereto by said ester.

3. A perfume composition comprising oil of petitgrain and as an extendertherefor, dihydroterpinyl acetate, the latter being present in an amountup to about 40% by weight of the total weight of said oil of petitgrainand said extender.

References Cited in the file of this patent Behal: Comptes Rendus, tome150, June 1910, pp. 17624.

Simonsen: The Terpenes, Cambridge Univ. Press, vol. 1, 2nd ed., revised1953, pp. 253, 254, 262.

Wertheim: Textbook of Organic Chcm., the Blakiston Co., Philadelphia,2nd ed., 1946, pp 50, 52.

in diethyl phthalate) 6

1. TOILET SOAP CONTAINING A MINOR AMOUNT OF DIHYDROTERPINYL ACETATESUFFICIENT TO IMPART TO SAID SOAP ODOR STABILITY, FRESHNESS ANDNATURALNESS.